Zr-BASED AMORPHOUS ALLOY AND METHOD OF PREPARING THE SAME

ABSTRACT

A Zr-based amorphous alloy and a method of preparing the same are provided. The Zr-based amorphous alloy is represented by the general formula of (Zr a M 1-a ) 100-x O x , in which a is an atomic fraction of Zr, and x is an atomic percent of O, in which: 0.3≦a≦0.9, and 0.02≦x≦0.6, and M may represent at least three elements selected from the group consisting of transition metals other than Zr, Group IIA metals, and Group IIIA metals in the Periodic Table of Elements.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to, and benefits of:

1) Chinese Patent Application No. 200910209456.8 filed with StateIntellectual Property Office, P. R. C. on Oct. 30, 2009; and

2) Chinese Patent Application No. 201010201008.6 filed with StateIntellectual Property Office, P. R. C. on May 31, 2010.

The entire contents of the above patent applications are incorporatedherein by reference.

FIELD

The present disclosure relates to an amorphous alloy, more particularlyto a Zr-based amorphous alloy and a method of preparing the same.

BACKGROUND

With the structure of long-range disorder but short-range order,amorphous alloys have excellent physical, chemical and mechanicalproperties, such as high strength, high hardness, high wear resistance,high corrosion resistance, high plasticity, high resistance, goodsuperconductivity, and low magnetic loss, thus having been applied in awide range of fields, such as mechanics, medical equipments, electrics,and military industries. Particularly, the discovery of bulk amorphousalloys greatly improves the research and the development of amorphousmaterials.

However, some inherent defects of the amorphous alloys may also hampertheir large-scale applications. For example, under load, amorphousalloys may not be deformed to resist the load, and finally may besuddenly broken when the stress reaches the fracture strength of theamorphous alloys, which seriously hampers the wide applications of theamorphous alloys. It has been found that the plastic deformation of anamorphous alloy may be obtained by adjusting compositions andmicro-structures of the amorphous alloy. Furthermore, the compositionsof the amorphous alloy are mainly metal elements, and oxygen may beregarded as a harmful element. Moreover, because less research has beendone on the method of preparing amorphous alloys, it is hard to achieveindustrial manufacturing of the amorphous alloys. Meanwhile, theperformance of the amorphous alloys also hampers their applications.

SUMMARY

In viewing thereof, the present disclosure is directed to solve at leastone of the problems existing in the prior art. Accordingly, a Zr-basedamorphous alloy may need to be provided with enhanced plasticity.Furthermore, a method of preparing the Zr-based amorphous alloy may alsoneed to be provided.

According to an aspect of the present disclosure, a Zr-based amorphousalloy represented by the general formula of (Zr_(a)M_(1-a))_(100-x)O_(x)is provided, in which: a is atomic fraction of Zr, and x is atomicpercent of O, in which: 0.3≦a≦0.9, and 0.02≦x≦0.6; and M represents atleast three elements selected from the group consisting of transitionmetals other than Zr, Group IIA metals, and Group IIIA metals in thePeriodic Table of Elements. In an alternative embodiment, 0.4≦a≦0.7;0.03≦x≦0.5; and M represents at least three elements selected from thegroup consisting of La series, Cu, Ag, Zn, Sc, Y, Ti, Zr, V, Nb, Ta, Cr,Mn, Fe, Co, Ni, Be, and Al, so that the Zr-based amorphous alloy mayhave enhanced plasticity.

In an embodiment, the Zr-based amorphous alloy may further possess atleast one of the following properties.

1). Based on the total volume of the Zr-based amorphous alloy, theZr-based amorphous alloy may have a crystalline phase of less than about70% by volume, and then the content of the amorphous phase will be morethan about 30% by volume.

2). The Zr-based amorphous alloy may have multiple dimension sizes withat least one dimension size less than about 5 mm, preferably about 2 mm.

3). The Zr-based amorphous alloy may have a plastic strain of more thanabout 1%.

In an alternative embodiment, based on the total volume of the Zr-basedamorphous alloy, the Zr-based amorphous alloy may have a crystallinephase of less than about 37% by volume, and then the content of theamorphous phase will be more than about 63% by volume.

According to another aspect of the present disclosure, a method ofpreparing a Zr-based amorphous alloy is provided. The method maycomprise the steps of: mixing raw materials comprising Zr and M with amolar ratio of a:(1−a) to form a mixture; heating the mixture to form amolten mixture; casting and cooling molding the molten mixture to formthe Zr-based amorphous alloy represented by the general formula of(Zr_(a)M_(1-a))_(100-x)O_(x), in which: a is atomic fraction of Zr and xis atomic percent of O, in which: 0.3≦a≦0.9, and 0.02≦x≦0.6; and Mrepresents at least three elements selected from the group consisting oftransition metals other than Zr, Group IIA metals, and Group IIIA metalsin the Periodic Table of Elements. The Zr-based amorphous alloy preparedby the method according to an embodiment of the present disclosure mayhave enhanced plasticity.

According to the alternative embodiments of the present disclosure, thecooling molding step may be performed in a mould with a thermalconductivity of about 10-400 W/m·K, preferably about 30-200 W/m·K. M mayrepresent at least three elements selected from the group consisting ofLa series, Cu, Ag, Zn, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Be,and Al. The casting temperature may be about 100° C. above the meltingtemperature of the Zr-based amorphous alloy. The mixing, heating, andcasting steps may be performed under a protective gas or under vacuum.The protective gas may be at least one gas selected from the groupconsisting of nitrogen and Group VIII gases in the Periodic Table ofElements, preferably nitrogen. The vacuum degree may be less than about1.01×10⁵ Pa. The cooling molding may be selected from gravity casting,suction casting, spray casting or die casting. The oxygen content may beacquired by well controlling the oxygen content in the raw materials andthe environment.

It has been found by the inventors that, plastic strain of the Zr-basedamorphous alloy may be enhanced by properly controlling the size and theoxygen content of the Zr-based amorphous alloy, the ratio of thecrystalline phase to the amorphous phase, and the preparing conditionsof the Zr-based amorphous alloy. The Zr-based amorphous alloy preparedby the method according to the present disclosure may have a plasticstrain of more than about 1%, thus improving the safety of the Zr-basedamorphous alloy when used as a structure part and broadening theapplication fields of the Zr-based amorphous alloy.

Additional aspects and advantages of the embodiments of the presentdisclosure will be given in part in the following descriptions, becomeapparent in part from the following descriptions, or be learned from thepractice of the embodiments of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other aspects and advantages of the present disclosure willbecome apparent and more readily appreciated from the followingdescriptions taken in conjunction with the drawings in which:

FIG. 1 shows a perspective view of a Zr-base amorphous alloy accordingto an embodiment of the present disclosure;

FIG. 2 shows stress-strain curves of samples C1-3 according to anembodiment of the present disclosure;

FIG. 3 shows XRD patterns of C1-3 and D3 according to an embodiment ofthe present disclosure; and

FIG. 4 shows a perspective view of an article made of Zr-based amorphousalloy according to an embodiment of the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENT

Reference will be made in detail to embodiments of the presentdisclosure. The embodiments described herein are explanatory,illustrative, and used to generally understand the present disclosure.The embodiments shall not be construed to limit the present disclosure.The same or similar elements and the elements having same or similarfunctions are denoted by like reference numerals throughout thedescriptions.

According to an aspect of the present disclosure, a Zr-based amorphousalloy represented by the general formula of (Zr_(a)M_(1-a))_(100-x)O_(x)is provided, in which a is atomic fraction of Zr, and x is atomicpercent of O, in which: and 0.3≦a≦0.9, and 0.02≦x≦0.6; and M representsat least three elements selected from the group consisting of transitionmetals other than Zr, Group IIA metals, and Group MA metals in thePeriodic Table of Elements. The Zr-based amorphous alloy may comprise acrystalline phase with a volume percent of less than about 70% and anamorphous phase with a volume percent of more than about 30%. TheZr-based amorphous alloy may have multiple dimension sizes with at leastone dimension size less than about 5 mm. The Zr-based amorphous alloymay have a plastic strain of more than about 1%.

In an alternative embodiment of the present disclosure, a Zr-basedamorphous alloy represented by the general formula of(Zr_(a)M_(1-a))_(100-x)O_(x) is provided, in which 0.4≦a≦0.7;0.03≦x≦0.5; and M represents at least three elements selected from thegroup consisting of La series, Cu, Ag, Zn, Sc, Y, Ti, Zr, V, Nb, Ta, Cr,Mn, Fe, Co, Ni, Be, and Al. The Zr-based amorphous alloy may have acrystalline phase with a volume percent of less than about 37% and anamorphous phase with a volume percent of more than about 63%. TheZr-based amorphous alloy may have multiple dimension sizes with at leastone dimension size less than about 2 mm.

It has been found by the inventors that, the compounding of materialsmay enhance the comprehensive performances of the materials, while thecompounding of the amorphous alloy materials has also been applied andresearched widely to enhance the comprehensive performances thereof. TheZr-based amorphous alloy according to the present disclosure maycomprise a crystalline phase with a volume percent of less than about70%, which may not affect the performances of the Zr-based amorphousalloy, but may improve the mechanical properties thereof. Furthermore,the Zr-based amorphous alloy may have multiple dimension sizes, thusforming various kinds of free volumes, atomic clusters, and shear zones.As for the shear zones, the Zr-based amorphous alloy according to thepresent disclosure may have at least one dimension size of less thanabout 5 mm, preferably about 2 mm. The multiple dimension sizes of theZr-based amorphous alloy may favor the increasing of the shear zones,and consequently may enhance the plastic deformability of the Zr-basedamorphous alloy. Moreover, compared with a conventional amorphous alloy,the micro-structure of the Zr-based amorphous alloy may improve themechanical properties of the Zr-based amorphous alloy, particularlystrength and plastic strain.

According to another aspect of the present disclosure, a method ofpreparing a Zr-based amorphous alloy may be provided. The method maycomprise the steps of: mixing raw materials comprising Zr and M with amolar ratio of a:(1−a) to form a mixture; heating the mixture to form amolten mixture; casting and cooling molding the molten mixture to formthe Zr-based amorphous alloy represented by the general formula of(Zr_(a)M_(1-a))_(100-x)O_(x), in which: a is atomic fraction of Zr, andx is atomic percent of O atomic fraction, in which: 0.3≦a≦0.9, and0.02≦x≦0.6. The mould may have a thermal conductivity of about 10-400W/m·K. M may be at least three elements selected from the groupconsisting of transition is metals other than Zr, Group IIA metals, andGroup IIIA metals in the Periodic Table of Elements. The castingtemperature may be about 100° C. above the melting temperature of theZr-based amorphous alloy.

In an alternative embodiment of the present disclosure, a method ofpreparing a Zr-based amorphous alloy may be provided. The method maycomprise the steps of: mixing raw materials comprising Zr and M with amolar ratio of a:(1−a) to form a mixture; heating the mixture to form amolten mixture; casting and cooling molding the molten mixture to formthe Zr-based amorphous alloy represented by the general formula of(Zr_(a)M_(1-a))_(100-x)O_(x), in which: 0.4≦a≦0.7, and 0.03≦x≦0.5. Themould may have a thermal conductivity of about 30-200 W/m·K. M may be atleast three elements selected from the group consisting of La series,Cu, Ag, Zn, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Be, and Al.The casting temperature may be about 100-500° C. above the meltingtemperature of the Zr-based amorphous alloy.

The melting temperature of the Zr-based amorphous alloy may be dependenton the composition of the Zr-based amorphous alloy, and may be tested bydifferential scanning calorimetry (DSC).

In an embodiment of the present disclosure, the Zr-based amorphous alloymay have multiple dimension sizes, with at least one dimension size lessthan about 5 mm, preferably about 2 mm.

The raw materials for forming the Zr-based amorphous alloy may compriseZr and M, and the composition of the Zr-based amorphous alloy may bevaried by adjusting the amounts of Zr and M and the oxygen content inthe raw materials. In an embodiment of the present disclosure, theZr-based amorphous alloy may be represented by the general formula of(Zr_(a)M_(1-a))_(100-x)O_(x), in which a is atomic fraction of Zr, and xis atomic percent of O, in which: 0.3≦a≦0.9, and 0.02≦x≦0.6, and Mrepresents at least three elements selected from the group consisting oftransition metals other than Zr, Group IIA metals, and Group IIIA metalsin the Periodic Table of Elements. The Zr-based amorphous alloy maycomprise a crystalline phase with a volume percent of less than about70% and an amorphous phase with a volume percent of more than about 30%.The Zr-based amorphous alloy may have multiple dimension sizes with atleast one dimension size less than about 5 mm. The Zr-based amorphousalloy may have a plastic strain of more than about 1%.

In an alternative embodiment of the present disclosure, the Zr-basedamorphous alloy may be represented by the general formula of(Zr_(a)M_(1-a))_(100-x)O_(x), in which 0.4≦a≦0.7; 0.03≦x≦0.5; and Mrepresents at least three elements selected from the group consisting ofLa series, Cu, Ag, Zn, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Be,and Al. The Zr-based amorphous alloy may have a crystalline phase with avolume percent of less than about 37% and an amorphous phase with avolume percent of more than about 63%. The Zr-based amorphous alloy mayhave multiple dimension sizes with at least one dimension size less thanabout 2 mm.

Oxygen in the amorphous alloy is generally considered as an impurity.Therefore, it has been considered that oxygen may not harm thecrystalline properties of the amorphous alloy only by controlling theoxygen content in the amorphous alloy to a low content, for example,less than about 1 atomic percent. In other words, the higher the purityof the raw materials, that is, the lower the content of the impurity,the better the performance of the amorphous alloy is. In this way, theadverse influence of oxygen or other impurities on the amorphous alloymay be reduced. However, it has been found by the inventors that, theplastic properties of the amorphous alloy may be significantly improvedby controlling the oxygen content in a range of about 0.02-0.6 atomicpercent, preferably about 0.03-0.5 atomic percent. In contrast, theamorphous alloy may exhibit poor plastic properties when the oxygencontent is out of this range.

In an embodiment, the raw materials may be mixed according to thechemical composition of the Zr-based amorphous alloy, and melted undervacuum or a protective gas. The required oxygen in the Zr-basedamorphous alloy may be provided by the oxygen in the raw materials andthe melting environment, in which the melting environment may include: amelting device, the protective gas during the melting step, and theremaining gas in the melting device. Oxygen may be in an atomic state,or a chemical state. As the amount of oxygen from the environment isless, the oxygen content in the Zr-based amorphous alloy may be mainlydetermined by the oxygen content in the raw materials. In an alternativeembodiment, the raw materials comprising Zr and M may have an oxygencontent of about 0.005-0.05 atomic percent. The extra small oxygencontent in the raw materials may cause an insufficient and unevendistribution of oxygen in the Zr-based amorphous alloy, whereas theextra large oxygen content in the raw materials may cause large amountsof oxygen in the Zr-based amorphous alloy, thus decreasing theperformance of the Zr-based amorphous alloy.

The purity of the raw materials may be varied according to differentZr-based amorphous alloys. In an embodiment, the purity of the rawmaterials may be more than about 99%, and the oxygen content in the rawmaterials may be about 0.005-0.05 atomic percent.

The vacuum condition may be known to those skilled in the art. In anembodiment, the vacuum degree may be less than about 1.01×10⁵ Pa. In analternative embodiment, the vacuum degree may be less than about 1000Pa. In a further alternative embodiment, the vacuum degree may be about3×10⁻⁵-10² Pa (absolute pressure).

The protective gas may be known to those skilled in the art, such as aninert gas selected from the group consisting of nitrogen, Group VIIIgases in the Periodic Table of Elements, and combinations thereof. Dueto the presence of a certain amount of oxygen in the Zr-based amorphousalloy, an inert gas with a concentration of no less than about 98% byvolume may meet the requirements.

The melting step may be achieved by any conventional melting method inthe art, provided that the raw materials for preparing the Zr-basedamorphous alloy are melted sufficiently, for example, melting in avacuum melting device. The melting temperature and the melting time maybe varied according to different raw materials. In an embodiment, themelting may be performed in a conventional vacuum melting device, suchas a vacuum arc melting furnace, a vacuum induction melting furnace, ora vacuum resistance furnace.

According to an embodiment of the present disclosure, the raw materialsmay be mixed to form a mixture; then the mixture may be heated to acasting temperature to form a molten mixture; and then cast and coolingmolded to form the Zr-based amorphous alloy. The higher the castingtemperature, the lower the required casting pressure is; whereas thelower the casting temperature, the higher the required casting pressureis. It has been found by the inventors that a Zr-based amorphous alloywith plastic strain may be obtained when the casting temperature isabout 100° C. above the melting temperature. In an alternativeembodiment, the casting temperature is about 100-500° C. above themelting temperature, to facilitate the casting step and the subsequentcooling molding steps. In a further alternative embodiment, the castingtemperature is about 100-200° C. above the melting temperature. Thecooling molding step may be achieved by any method well-known in theart, such as a casting method. In some embodiment, the casting may beselected from gravity casting, suction casting, spray casting or diecasting. In a further embodiment, the casting may be high pressurecasting. The process and the condition of the high pressure casting maybe well-known in the art. For example, the high pressure casting may beperformed under a pressure of about 2-20 MPa.

According to an embodiment of the present disclosure, the high pressurecasting may be performed in a mould, and the mould may be anyconventional one in the art. The cooling speed during the coolingmolding step may be well controlled by using a mould with suitablethermal conductivity, thus obtaining a Zr-based amorphous alloy withstable properties. In an embodiment, the mould may have a thermalconductivity of about 10-400 W/m·K. In an alternative embodiment, themould may have a thermal conductivity of about 30-200 W/m·K.Furthermore, a Zr-based amorphous alloy with a certain size may beobtained by changing the cavity of the mould. In this way, the Zr-basedamorphous alloy with at least one dimension size of less than about 5 mmmay be obtained.

According to an embodiment of the present disclosure, the mould maycooled by water or oil. There are no special limits on the coolingdegree of the molten mixture, provided that the Zr-based amorphous alloyis formed.

The following provides additional details of some embodiments of thepresent disclosure.

EMBODIMENT 1

A method of preparing a Zr-based amorphous alloy comprises the followingsteps.

a) 100 g of raw materials comprising Zr with an oxygen content of about0.005 atomic percent, Ti with an oxygen content of about 0.01 atomicpercent, Cu with an oxygen content of about 0.005 atomic percent, Niwith an oxygen content of about 0.005 atomic percent, and Be with anoxygen content of about 0.005 atomic percent according to thecomposition of the Zr-based amorphous alloy were placed in a vacuuminduction furnace. The vacuum induction furnace was vacuumized to avacuum degree of about 50 Pa, then argon with a purity of about 99% byvolume was filled in the vacuum induction furnace. The raw materialswere melted sufficiently at a temperature of about 1500° C., then castinto an ingot. The ingot was tested by inductively coupled plasma (ICP)analysis and oxygen content analysis to obtain a composition of(Zr_(0.41)Ti_(0.14)Co_(0.15)Ni_(0.10)Be_(0.20))_(99.925)O_(0.075).

b) The ingot was heated to a casting temperature of about 805° C., thendie-cast under a casting pressure of about 5 MPa in a mould with athermal conductivity of about 60 W/m·K. The cast ingot was molded withcooling to form the Zr-based amorphous alloy sample C1 with a size ofabout 180 mm×10 mm×2 mm. The melting temperature of the Zr-basedamorphous alloy sample C1 is about 705° C.

COMPARATIVE EMBODIMENT 1

A method of preparing a Zr-based amorphous alloy comprises the followingsteps.

a) 100 g of raw materials comprising Zr with an oxygen content of about0.003 atomic percent, Ti with an oxygen content of about 0.003 atomicpercent, Cu with an oxygen content of about 0.005 atomic percent, Niwith an oxygen content of about 0.002 atomic percent, and Be with anoxygen content of about 0.005 atomic percent according to thecomposition of the Zr-based amorphous alloy were placed in a vacuuminduction furnace. The vacuum induction furnace was vacuumized to avacuum degree of about 50 Pa, then argon with a purity of about 99% byvolume was filled in the vacuum induction furnace. The raw materialswere melted sufficiently at a temperature of about 1500° C., then castinto an ingot. The ingot was tested by inductively coupled plasma (ICP)analysis and oxygen content analysis to obtain a composition of(Zr_(0.41)Ti_(0.14)Cu_(0.15)Ni_(0.10)Be_(0.20))99.99O_(0.01).

b) The ingot was heated to a casting temperature of about 805° C., thendie-cast under a casting pressure of about 5 MPa in a mould with athermal conductivity of about 60 W/m·K. The cast ingot was molded withcooling to form the Zr-based amorphous alloy sample D1 with a size ofabout 180 mm×10 mm×6 mm. The melting temperature of the Zr-basedamorphous alloy sample D1 is about 705° C.

EMBODIMENT 2

A method of preparing a Zr-based amorphous alloy comprises the followingsteps.

a) 100 g of raw materials comprising Zr with an oxygen content of about0.005 atomic percent, Al with an oxygen content of about 0.01 atomicpercent, Cu with an oxygen content of about 0.005 atomic percent, and Niwith an oxygen content of about 0.006 atomic percent according to thecomposition of the Zr-based amorphous alloy were placed in a vacuuminduction furnace. The vacuum induction furnace was vacuumized to avacuum degree of about 0.1 Pa, then argon with a purity of about 99% byvolume was filled in the vacuum induction furnace. The raw materialswere melted sufficiently at a temperature of about 1500° C., then castinto an ingot. The ingot was tested by inductively coupled plasma (ICP)analysis and oxygen content analysis to obtain a composition of(Zr_(0.55)Al_(0.15)Cu_(0.25)Ni_(0.05))_(99.955)O_(0.045).

b) The ingot was heated to a casting temperature of about 950° C., thendie-cast under a casting pressure of about 5 MPa in a mould with athermal conductivity of about 100 W/m·K. The cast ingot was molded withcooling to form the Zr-based amorphous alloy sample C2 with a size ofabout 180 mm×10 mm×1 mm. The melting temperature of the Zr-basedamorphous alloy sample C2 is about 840° C.

COMPARATIVE EMBODIMENT 2

A method of preparing a Zr-based amorphous alloy comprises the followingsteps.

a) 100 g of raw materials comprising Zr with an oxygen content of about0.08 atomic percent, Al with an oxygen content of about 0.01 atomicpercent, Cu with an oxygen content of about 0.005 atomic percent, and Niwith an oxygen content of about 0.08 atomic percent according to thecomposition of the Zr-based amorphous alloy were placed in a vacuuminduction furnace. The vacuum induction furnace was vacuumized to avacuum degree of about 500 Pa, then argon with a purity of about 95% byvolume was filled in the vacuum induction furnace. The raw materialswere melted sufficiently at a temperature of about 1500° C., then castinto an ingot. The ingot was tested by inductively coupled plasma (ICP)analysis and oxygen content analysis to obtain a composition of(Zr_(0.55)Al_(0.15)Cu_(0.25)Ni_(0.05))_(98.9)O_(1.1).

b) The ingot was heated to a casting temperature of about 950° C., thendie-cast under a casting pressure of about 5 MPa in a mould with athermal conductivity of about 100 W/m·K. The cast ingot was molded withcooling to form the Zr-based amorphous alloy sample D1 with a size ofabout 180 mm×10 mm×1 mm. The melting temperature of the Zr-basedamorphous alloy sample D2 is about 840° C.

EMBODIMENT 3

A method of preparing a Zr-based amorphous alloy comprises the followingsteps.

a) 100 g of raw materials comprising Zr with an oxygen content of about0.003 atomic percent, Ti with an oxygen content of about 0.005 atomicpercent, Nb with an oxygen content of about 0.005 atomic percent, Cuwith an oxygen content of about 0.005 atomic percent, Ni with an oxygencontent of about 0.008 atomic percent, and Be with an oxygen content ofabout 0.02 atomic percent according to the composition of the Zr-basedamorphous alloy were placed in a vacuum induction furnace. The vacuuminduction furnace was vacuumized to a vacuum degree of about 50 Pa, thenargon with a purity of about 99% by volume was filled in the vacuuminduction furnace. The raw materials were melted sufficiently at atemperature of about 1500° C., then cast into an ingot. The ingot wastested by inductively coupled plasma (ICP) analysis and oxygen contentanalysis to obtain a composition of(Zr_(0.56)Ti_(0.14)Nb_(0.05)Cu_(0.07)Ni_(0.06)Be_(0.12))_(99.965)O_(0.035).

b) The ingot was remelted and heated to a casting temperature of about900° C., then die-cast under a casting pressure of about 5 MPa in amould with a thermal conductivity of about 150 W/m·K. The cast ingot wasmolded with cooling to form the Zr-based amorphous alloy sample C3 witha size of about 180 mm×10 mm×0.5 mm. The melting temperature of theZr-based amorphous alloy sample C3 is about 718° C.

COMPARATIVE EMBODIMENT 3

A method of preparing a Zr-based amorphous alloy comprises the followingsteps.

a) 100 g of raw materials comprising Zr with an oxygen content of about0.003 atomic percent, Ti with an oxygen content of about 0.003 atomicpercent, Nb with an oxygen content of about 0.005 atomic percent, Cuwith an oxygen content of about 0.005 atomic percent, Ni with an oxygencontent of about 0.002 atomic percent, and Be with an oxygen content ofabout 0.005 atomic percent according to the composition of the Zr-basedamorphous alloy were placed in a vacuum induction furnace. The vacuuminduction furnace was vacuumized to a vacuum degree of about 50 Pa, thenargon with a purity of about 99% by volume was filled in the vacuuminduction furnace. The raw materials were melted sufficiently at atemperature of about 1500° C., then cast into an ingot. The ingot wastested by inductively coupled plasma (ICP) analysis and oxygen contentanalysis to obtain a composition of(Zr_(0.345)Ti_(0.115)Nb_(0.09)Cu_(0.125)Ni_(0.1)Be_(0.225))_(99.2)O_(0.8).

b) The ingot was remelted and heated to a casting temperature of about900° C., then die-cast under a casting pressure of about 5 MPa in amould with a thermal conductivity of about 5 W/m·K. The cast ingot wasmolded with cooling form the Zr-based amorphous alloy sample D3 with asize of about 180 mm×10 mm×0.5 mm. The melting temperature of theZr-based amorphous alloy sample D3 is about 718° C.

EMBODIMENT 4

A method of preparing a Zr-based amorphous alloy comprises the followingsteps.

a) 100 g of raw materials comprising Zr with an oxygen content of about0.005 atomic percent, Ti with an oxygen content of about 0.04 atomicpercent, Nb with an oxygen content of about 0.005 atomic percent, Cuwith an oxygen content of about 0.03 atomic percent, Ni with an oxygencontent of about 0.02 atomic percent, and Be with an oxygen content ofabout 0.014 atomic percent according to the composition of the Zr-basedamorphous alloy were placed in a vacuum induction furnace. The vacuuminduction furnace was vacuumized to a vacuum degree of about 50 Pa, thenargon with a purity of about 99% by volume was filled in the vacuuminduction furnace. The raw materials were melted sufficiently at atemperature of about 1500° C., then cast into an ingot. The ingot wastested by inductively coupled plasma (ICP) analysis and oxygen contentanalysis to obtain a composition of(Zr_(0.65)Ti_(0.05)Nb_(0.05)Cu_(0.08)Ni_(0.07)Be_(0.05))_(99.875)O_(0.125).

b) The ingot was remelted and heated to a casting temperature of about855° C., then die-cast under a casting pressure of about 5 MPa in amould with a thermal conductivity of about 200 W/m·K. The cast ingot wasmolded with cooling to form the Zr-based amorphous alloy sample C4 witha size of about 180 mm×10 mm×1 mm. The melting temperature of theZr-based amorphous alloy sample C4 is about 750° C.

EMBODIMENT 5

A method of preparing a Zr-based amorphous alloy comprises the followingsteps.

a) 100 g of raw materials comprising Zr with an oxygen content of about0.03 atomic percent, Ti with an oxygen content of about 0.005 atomicpercent, Nb with an oxygen content of about 0.005 atomic percent, Cuwith an oxygen content of about 0.009 atomic percent, Ni with an oxygencontent of about 0.004 atomic percent, and Be with an oxygen content ofabout 0.007 atomic percent according to the composition of the Zr-basedamorphous alloy were placed in a vacuum induction furnace. The vacuuminduction furnace was vacuumized to a vacuum degree of about 50 Pa, thenargon with a purity of about 99% by volume was filled in the vacuuminduction furnace. The raw materials were melted sufficiently at atemperature of about 1500° C., then cast into an ingot. The ingot wastested by inductively coupled plasma (ICP) analysis and oxygen contentanalysis to obtain a composition of(Zr_(0.07)Ti_(0.06)Nb_(0.05)Cu_(0.05)Ni_(0.06)Be_(0.06))_(99.545)O_(0.455).

b) The ingot was remelted and heated to a casting temperature of about850° C., then die-cast under a casting pressure of about 5 MPa in amould with a thermal conductivity of about 200 W/m·K. The cast ingot wasmolded with cooling to form the Zr-based amorphous alloy sample C5 witha size of about 180 mm×10 mm×1 mm. The melting temperature of theZr-based amorphous alloy sample C5 is about 744° C.

EMBODIMENT 6

A method of preparing a Zr-based amorphous alloy comprises the followingsteps.

a) 100 g of raw materials comprising Zr with an oxygen content of about0.01 atomic percent, Nb with an oxygen content of about 0.005 atomicpercent, Cu with an oxygen content of about 0.005 atomic percent, Niwith an oxygen content of about 0.005 atomic percent, Co with an oxygencontent of about 0.005 atomic percent, Fe with an oxygen content ofabout 0.005 atomic percent, and Be with an oxygen content of about 0.005atomic percent according to the composition of the Zr-based amorphousalloy were placed in a vacuum induction furnace. The vacuum inductionfurnace was vacuumized to a vacuum degree of about 50 Pa, then argonwith a purity of about 99% by volume was filled in the vacuum inductionfurnace. The raw materials were melted sufficiently at a temperature ofabout 1500° C., then cast into an ingot. The ingot was tested byinductively coupled plasma (ICP) analysis and oxygen content analysis toobtain a composition of(Zr0.57Ti_(0.06)Nb_(0.05)Cu_(0.05)Ni_(0.08)Co_(0.05)Fe_(0.08)Be_(0.06))_(99.45)O_(0.55).

b) The ingot was remelted and heated to a casting temperature of about950° C., then die-cast under a casting pressure of about 5 MPa in amould with a thermal conductivity of about 150 W/m·K. The cast ingot wasmolded with cooling to form the Zr-based amorphous alloy sample C6 witha size of about 180 mm×10 mm×4 mm. The melting temperature of theZr-based amorphous alloy sample C6 is about 827° C.

Test

1) ICP

The Zr-based amorphous alloy samples C1-6 and D1-3 were respectivelytested on an iCAP6300-CPA Inductively Coupled Plasma Atomic EmissionSpectrometer (ICP-AES) under the conditions of: a wavelength of about166-847 nm, a focal length of about 383 nm, a resolution of about 0.007nm at a distance of about 200 nm, and a detection limit of about0.002-0.2 g/L.

The testing results were shown in Table 1.

2) Oxygen Content

The Zr-based amorphous alloy samples C1-6 and D1-3 were respectivelytested on an IRO-II infrared oxygen content analyzer commerciallyavailable from Beijing NCS Analytical Instruments Co., Ltd. by acombustion method, using argon as a protective gas, while the cruciblewas made of graphite.

3) Bending Strength

The Zr-based amorphous alloy samples C1-6 and D1-3 were respectivelytested on a CMT5000 testing machine with a tonnage of about 100 toncommercially available from Shenzhen Sans Testing Machine Co., Ltd.,P.R.C. under the conditions of a loading speed of about 0.5 mm/min and aspan of about 50 mm, to obtain the bending strength of the Zr-basedamorphous alloys C1-6 and D1-3, thus obtaining the plastic strain datathereof. The testing results were shown in Table 1. The stress-straincurves of the Zr-based based amorphous alloy samples C1-3 were shown inFIG. 2.

4) XRD

The Zr-based amorphous alloy samples C1-3 and D3 were respectivelytested on a D-MAX2200PC X-ray powder diffactometer under the conditionsof: a copper target, an incident wavelength of about 1.54060 Å, anaccelerating voltage of about 40 KV, a current of about 20 mA, and ascanning step of about 0.04°. The XRD patterns of the Zr-based amorphousalloy samples C1-3 and D3 were shown in FIG. 3.

5) DSC

The Zr-based amorphous alloy samples C1-6 and D1-3 were respectivelytested on a NETZSCH STA 449C machine commercially available from NETZSCHInstruments Co., Ltd., Germany, under the conditions of: a heating rateof about 50 K/min, and a sample weight of about 1000 mg, using argon asa protective gas. The melting temperature of each Zr-based amorphousalloy sample may be determined by the DSC pattern thereof. The testingresults were shown in Table 1.

TABLE 1 Melting Casting Percent of Percent of Thermal PlasticTemperature Temperature Crystalline Amorphous Oxygen Conductivity Size(Length × Strain No. (° C.) (° C.) Phase (%) Phase (%) Content (W/m · K)Width × Height) (%) C1 705 805 5 95 0.075 60 180 × 10 × 2 37.5 C2 840950 5 95 0.045 100 180 × 10 × 1 7 C3 718 900 30 70 0.035 150 180 × 10 ×0.5 8 C4 750 855 25 75 0.125 200 180 × 10 × 1 4 C5 744 850 14 86 0.455200 180 × 10 × 1 3.5 C6 827 950 23 77 0.55 150 180 × 10 × 4 3.5 D1 705805 5 95 0.01 60 180 × 10 × 6 0.3 D2 840 950 5 95 1.1 100 180 × 10 × 10.2 D3 718 900 40 60 0.8 5 180 × 10 × 0.5 0.5

As shown in Table 1, the Zr-based amorphous alloy according to thepresent disclosure may have enhanced plastic properties by wellcontrolling the composition and the oxygen content of the Zr-basedamorphous alloy, the casting temperature, the cooling condition, and thesize of the Zr-based amorphous alloy.

The Zr-based amorphous alloy according to the present disclosure mayhave multiple dimension sizes with at least one dimension size of noless than about 5 mm, preferably about 2 mm, which may be applied invarious fields such as precision instruments and sports instruments. TheZr-based amorphous alloy according to the present disclosure may haveexcellent properties, such as excellent elasticity recovery capability,certain plastic deformability, excellent wear resistance and excellentcorrosion resistance, and consequently may be formed into various shapesand structures, including, but not limited to, an article shown in FIG.4.

Although the present disclosure have been described in detail withreference to several embodiments, additional variations andmodifications exist within the scope and spirit as described and definedin the following claims.

1. A Zr-based amorphous alloy having a formula of:(Zr_(a)M_(1-a))_(100-x)O_(x), wherein: a is an atomic fraction of Zr,and x is an atomic percent of oxygen, in which: 0.3≦a≦0.9, and0.02≦x≦0.6; and M represents at least three elements selected from thegroup consisting of transition metals other than Zr, Group IIA metals,and Group IIIA metals .
 2. The Zr-based amorphous alloy of claim 1,wherein the Zr-based amorphous alloy has a crystalline phase of lessthan about 70% by volume based on the total volume of the Zr-basedamorphous alloy; multiple dimension sizes with at least one dimensionsize less than about 5 mm; and a plastic strain of more than about 1%.3. The Zr-based amorphous alloy of claim 2, wherein the Zr-basedamorphous alloy has a crystalline phase of less than about 37% by volumebased on the total volume of the Zr-based amorphous alloy.
 4. TheZr-based amorphous alloy of claim 2, wherein the Zr-based amorphousalloy has multiple dimension sizes with at least one dimension size lessthan about 2 mm.
 5. The Zr-based amorphous alloy of claim 1, wherein:0.4≦a≦0.7; 0.03≦x≦0.5; and M represents at least three elements selectedfrom the group consisting of La series, Cu, Ag, Zn, Sc, Y, Ti, Zr, V,Nb, Ta, Cr, Mn, Fe, Co, Ni, Be, and Al.
 6. A method comprising: mixingraw materials comprising Zr and M with a molar ratio of a:(1−a) to forma mixture; heating the mixture to form a molten mixture; casting andcold molding the molten mixture to form the Zr-based amorphous alloy ofclaim
 1. 7. The method of claim 6, wherein the mixing, heating, andcasting steps are performed under a protective gas or vacuum.
 8. Themethod of claim 7, wherein the protective gas is at least one gasselected from the group consisting of nitrogen and Group XVIII gases. 9.The method of claim 6, wherein the cooling molding step is performed ina mold with a thermal conductivity ranging from about 10 W/m·K to about400 W/m·K.
 10. The method of claim 9, wherein the cooling molding stepis performed in a mold with a thermal conductivity ranging from about 30W/m·K to about 200 W/m·K. 11 . The method of claim 6, wherein thecasting step is performed under a casting temperature of about 100° C.above the melting temperature of the Zr-based amorphous alloy.
 12. Themethod of claim 11, wherein the casting step is performed under acasting temperature ranging from about 100° C. to about 500° C. abovethe melting temperature of the Zr-based amorphous alloy.
 13. The methodof claim 6, wherein the Zr-based amorphous alloy has multiple dimensionsizes with at least one dimension size less than about 2 mm.
 14. Themethod of claim 6, wherein: 0.4≦a≦0.7; 0.3≦x≦0.5; and M represents atleast three elements selected from the group consisting of La series,Cu, Ag, Zn, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Be, and Al.15. The method of claim 6, wherein the cold molding is selected from thegroup consisting of: gravity casting, suction casting, spray casting anddie casting.